The tenacious symmetry breaking of the electronic wave function of the nitrate radical (NO3) and its effect on the ground-state potential energy surface is investigated in detail. The symmetry breaking of Hartree-Fock wave functions results from a dominance of the orbital localization effect over the resonance effect and leads to three different solutions, one symmetrical and two distorted ones, for the same electronic state. The respective equilibrium geometries of these solutions are points on different potential surfaces, making their comparison meaningless. The resonance effect is promoted by dynamic as well as static electron correlation. However, the dynamic correlation methods [e.g., many-body perturbation theory (MBPT) and coupled-cluster single double (CCSD)] cannot overcome the symmetry breaking of the reference function and the problem of multiple solutions persists. The symmetry breaking can be avoided by the complete active space self-consistent field (CASSCF) approach that yields unique, single-valued surfaces for all electronic states. However, a sufficiently large and appropriately selected active space has to be used to avoid unphysical distortion of the wave function. Still the orbital localization effect leads to equilibrium geometries of C-2v symmetry which strongly depend on the state-averaging of the CASSCF wave function. Multireference single double configuration interaction (MR-SDCI) wave functions are also free of symmetry breaking, if the reference orbitals are and if the configuration space is invariant under the symmetry operations. MRCI geometry optimizations only result in D-3h symmetric structures with bond lengths and harmonic frequencies in close agreement with experimental data.